There is a need for improved polymeric materials that are highly permeable, yet may under certain circumstances, provide selective separation of various gas combinations. Such materials would especially be useful in commercial, non-cryogenic gas separation processes.
The commercial application for gas separation devices based on polymeric materials relies, in part, on maximizing the overall gas flux through the membrane. P. H. Kim, et al., J. Appl. Poly. Sci., 34 1761 (1987), reported that the gas flux for a membrane is relatable to the average space between the polymer chains. In addition, they indicated that the density of the polymer is also related to the overall gas flux. The problem, in part, for these commercial applications is to identify polymers with very high flux and with good thermo-mechanical properties. It has generally been observed that to achieve high overall flux requires having a polymer with low chain-chain interactions. This can be exemplified by polymers such as poly(dimethylsiloxane) or poly(4-methyl-1-pentene). These materials have rather high gas flux values. These high flux materials have, because of their low chain-chain interaction, low glass transition temperatures (Tg). As a consequence, these materials require either special processing conditions to build in chemical and physiochemical crosslinking or they can be used only at rather low application temperatures. By contrast, polymers with strong chain-chain interactions have rather high Tg values and have usually exhibited rather low gas flux.
U.S. Pat. Nos. 3,822,202 and 3,899,309; Re 30,351 (1980), disclose a process for separating fluids using a semi-permeable membrane made from polyimides, polyesters or polyamides. The repeating units of the main polymer chain of these membranes are distinguished in that such repeating units have at least one rigid divalent subunit, the two main chain single bonds extending from which are not collinear, is sterically unable to rotate 360.degree. around at least one of these bonds, and has 50% or more of its main chain atoms as members of aromatic rings.
U.S. Pat. No. 4,705,540 discloses a highly permeable aromatic polyimide gas separation membrane and processes for using said membrane. The membrane is an aromatic polyimide membrane in which the phenylenediamines are rigid and are substituted on essentially all of the positions ortho to the amino substituents, and the acid anhydride groups are essentially all attached to rigid aromatic moieties.
U.S. Pat. Nos. 4,717,393 and 4,717,394 disclose polymeric membranes and processes using the membranes for separating components of a gas mixture. The membranes disclosed in both of these patents are semi-flexible, aromatic polyimides, prepared by polycondensation of dianhydrides with phenylenediamines having alkyl substituents on all ortho positions to the amine functions, or with mixtures of other, non-alkylated diamines, some components have substituents on all positions ortho to the amine functions. It is taught that the membranes formed from this class of polyimides exhibit improved environmental stability and gas permeability, due to the optimization of the molecular free volume in the polymer.
U.S. Pat. No. 4,378,400 discloses gas separation membranes formed from aromatic polyimides based upon biphenyltetra-carboxylic dianhydride for separating various mixtures. Japanese Patent Application 1-194905 discloses gas separation membranes formed from various polyimides and Japanese Patent Applicaitons 63-190607 and 63-278524 disclose gas separation membranes formed from various polyamides. Japanese Patent Application 1-194904 discloses gas separation membranes formed from polyarylates having hydrogen, methyl, or ethyl groups on all positions ortho to the hydroxy functions. Such membranes are reported to have O.sub.2 /N.sub.2 selectivities from 1.7 to 2.5.
U.S. Pat. No. 4,840,646 and related E. P. Application 87303339.3 disclose tetrabromo bisphenol based polyestercarbonate membranes. The bisphenols contain linking groups selected form --C.dbd.O--, --SO.sub.2 --, and --O--.
M. Salame in Poly. Eng. Sci., 26 1543 (1986) developed a predictive relationship for oxygen permeability coefficient [(PO.sub.2)] and polymer structure. In the publication he demonstrates the group contributions of structural portions of a polymer to P(O.sub.2) values. In particular he indicates the presence of an aromatic group; i.e. phenyl, in place of methylene decreases the P(O.sub.2) values for a pair of comparative polymers.
N. Muruganandam, et al., J. Polym. Phy. 25, 1999 (1987) described the effects of alkylated and halogenated polymer material on oxygen and nitrogen permeability and permselectivity. Their results indicated that controlling the polymeric chain-chain packing and intramolecular torsional mobility can improve the performance of polymeric membranes
U.S. Pat. Nos. 5,007,945 and 5,013,332 disclose a class of polymeric membranes formed from aromatic polyarylates derived from dicarboxylic acid chlorides and cardo or cyclohexyl bisphenols, respectively, having halo or methyl substituents on all positions ortho to the hydroxy functions.